Semiconductor device and manufacturing method thereof

ABSTRACT

A method of manufacturing a semiconductor device includes forming an alloy semiconductor material layer comprising a first element and a second element on a semiconductor substrate. A mask is formed on the alloy semiconductor material layer to provide a masked portion and an unmasked portion of the alloy semiconductor material layer. The unmasked portion of the alloy semiconductor material layer not covered by the mask is irradiated with radiation from a radiation source to transform the alloy semiconductor material layer so that a surface region of the unmasked portion of the alloy semiconductor material layer has a higher concentration of the second element than an internal region of the unmasked portion of the alloy semiconductor material layer. The surface region surrounds the internal region.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.16/687,055, filed on Nov. 18, 2019, now U.S. Pat. No. 11,063,149, whichis a Divisional of U.S. patent application Ser. No. 15/644,597, filed onJul. 7, 2017, now U.S. Pat. No. 10,510,888, which claims priority toU.S. Provisional Application No. 62/427,648 filed on Nov. 29, 2016, theentire disclosure of the three applications are incorporated herein byreference.

BACKGROUND

As the semiconductor industry has progressed into nanometer technologyprocess nodes in pursuit of higher device density, higher performance,and lower costs, challenges from both fabrication and design issues haveresulted in the development of three-dimensional designs, such as amulti-gate field effect transistor (FET) including a fin FET (FinFET).As devices become smaller and corresponding electrical contact areashrinks, contact resistance increases, and device performance isimpacted. It is desirable to reduce contact resistance and improveelectron flow in semiconductor devices.

BRIEF DESCRIPTION OF THE DRAWINGS

The present disclosure is best understood from the following detaileddescription when read with the accompanying figures. It is emphasizedthat, in accordance with the standard practice in the industry, variousfeatures are not drawn to scale and are used for illustration purposesonly. In fact, the dimensions of the various features may be arbitrarilyincreased or reduced for clarity of discussion.

FIG. 1 is a cross-sectional view of an exemplary sequential operation ina method of manufacturing a semiconductor device according to anembodiment of the present disclosure.

FIG. 2 is a cross-sectional view of an exemplary sequential operation ina method of manufacturing a semiconductor device according to anembodiment of the present disclosure.

FIG. 3 is a cross-sectional view of an exemplary sequential operation ina method of manufacturing a semiconductor device according to anembodiment of the present disclosure.

FIG. 4 is a cross-sectional view of an exemplary sequential operation ina method of manufacturing a semiconductor device according to anembodiment of the present disclosure.

FIG. 5 is a cross-sectional view of an exemplary sequential operation ina method of manufacturing a semiconductor device according to anembodiment of the present disclosure.

FIG. 6 is a cross-sectional view of an exemplary sequential operation ina method of manufacturing a semiconductor device according to anembodiment of the present disclosure.

FIG. 7 is a cross-sectional view of an exemplary sequential operation ina method of manufacturing a semiconductor device according to anembodiment of the present disclosure.

FIG. 8 is a cross-sectional view of an exemplary sequential operation ina method of manufacturing a semiconductor device according to anembodiment of the present disclosure.

FIG. 9 is a cross-sectional view of an exemplary sequential operation ina method of manufacturing a semiconductor device according to anembodiment of the present disclosure.

FIG. 10 is a cross-sectional view of an exemplary sequential operationin a method of manufacturing a semiconductor device according to anembodiment of the present disclosure.

FIG. 11 is a cross-sectional view of an exemplary sequential operationin a method of manufacturing a semiconductor device according to anembodiment of the present disclosure.

FIG. 12 is a cross-sectional view of an exemplary sequential operationin a method of manufacturing a semiconductor device according to anembodiment of the present disclosure.

FIG. 13 is a cross-sectional view of an exemplary sequential operationin a method of manufacturing a semiconductor device according to anembodiment of the present disclosure.

FIG. 14 is a cross-sectional view of an exemplary sequential operationin a method of manufacturing a semiconductor device according to anembodiment of the present disclosure.

FIG. 15 is a cross-sectional view of an exemplary sequential operationin a method of manufacturing a semiconductor device according to anembodiment of the present disclosure.

FIG. 16 is a cross-sectional view of an exemplary sequential operationin a method of manufacturing a semiconductor device according to anembodiment of the present disclosure.

FIG. 17 is a cross-sectional view of an exemplary sequential operationin a method of manufacturing a semiconductor device according to anembodiment of the present disclosure.

FIG. 18 is an isometric view of an exemplary sequential operation in amethod of manufacturing a complementary metal oxide semiconductor (CMOS)FinFET device according to an embodiment of the present disclosure.

FIG. 19 is an isometric view of an exemplary sequential operation in amethod of manufacturing a CMOS FinFET device according to an embodimentof the present disclosure.

FIG. 20 is an isometric view of an exemplary sequential operation in amethod of manufacturing a CMOS FinFET device according to an embodimentof the present disclosure.

FIG. 21 is an isometric view of an exemplary sequential operation in amethod of manufacturing a CMOS FinFET device according to an embodimentof the present disclosure.

FIG. 22 is an isometric view of an exemplary sequential operation in amethod of manufacturing a CMOS FinFET device according to an embodimentof the present disclosure.

FIG. 23 is a cross-sectional view of an exemplary sequential operationin a method of manufacturing a semiconductor device according to anembodiment of the present disclosure.

FIG. 24 is a cross-sectional view of an exemplary sequential operationin a method of manufacturing a semiconductor device according to anembodiment of the present disclosure.

FIG. 25 is a cross-sectional view of an exemplary sequential operationin a method of manufacturing a semiconductor device according to anembodiment of the present disclosure.

FIG. 26 is a cross-sectional view of an exemplary sequential operationin a method of manufacturing a semiconductor device according to anembodiment of the present disclosure.

FIG. 27 is a cross-sectional view of an exemplary sequential operationin a method of manufacturing a semiconductor device according to anembodiment of the present disclosure.

FIG. 28 is a cross-sectional view of an exemplary sequential operationin a method of manufacturing a semiconductor device according to anembodiment of the present disclosure.

FIG. 29 is a cross-sectional view of an exemplary sequential operationin a method of manufacturing a semiconductor device according to anembodiment of the present disclosure.

FIG. 30 is a cross-sectional view of an exemplary sequential operationin a method of manufacturing a semiconductor device according to anembodiment of the present disclosure.

FIG. 31 is an isometric view of an exemplary sequential operation in amethod of manufacturing a CMOS FinFET device according to an embodimentof the present disclosure.

FIG. 32 is an isometric view of an exemplary sequential operation in amethod of manufacturing a CMOS FinFET device according to an embodimentof the present disclosure.

FIG. 33 is an isometric view of an exemplary sequential operation in amethod of manufacturing a CMOS FinFET device according to an embodimentof the present disclosure.

FIG. 34 is an isometric view of an exemplary sequential operation in amethod of manufacturing a CMOS FinFET device according to an embodimentof the present disclosure.

FIG. 35 is an isometric view of an exemplary sequential operation in amethod of manufacturing a CMOS FinFET device according to an embodimentof the present disclosure.

FIG. 36 is a plan view of an exemplary semiconductor device according toan embodiment of the present disclosure.

FIG. 37 is a plan view of an exemplary semiconductor device according toan embodiment of the present disclosure.

FIG. 38 is a view of an exemplary operation in a method of manufacturinga semiconductor device according to an embodiment of the presentdisclosure.

FIG. 39 is a view of an exemplary operation in a method of manufacturinga semiconductor device according to an embodiment of the presentdisclosure.

DETAILED DESCRIPTION

It is to be understood that the following disclosure provides manydifferent embodiments, or examples, for implementing different featuresof the invention. Specific embodiments or examples of components andarrangements are described below to simplify the present disclosure.These are, of course, merely examples and are not intended to belimiting. For example, dimensions of elements are not limited to thedisclosed range or values, but may depend upon process conditions and/ordesired properties of the device. Moreover, the formation of a firstfeature over or on a second feature in the description that follows mayinclude embodiments in which the first and second features are formed indirect contact, and may also include embodiments in which additionalfeatures may be formed interposing the first and second features, suchthat the first and second features may not be in direct contact. Variousfeatures may be arbitrarily drawn in different scales for simplicity andclarity.

Further, spatially relative terms, such as “beneath,” “below,” “lower,”“above,” “upper” and the like, may be used herein for ease ofdescription to describe one element or feature's relationship to anotherelement(s) or feature(s) as illustrated in the figures. The spatiallyrelative terms are intended to encompass different orientations of thedevice in use or operation in addition to the orientation depicted inthe figures. The device may be otherwise oriented (rotated 90 degrees orat other orientations) and the spatially relative descriptors usedherein may likewise be interpreted accordingly. In addition, the term“made of” may mean either “comprising” or “consisting of.”

FIGS. 1 to 8 are cross-sectional views of exemplary sequentialoperations in a method of manufacturing a semiconductor device 10according to an embodiment of the present disclosure. As shown in FIG.1, isolation insulating layers 14, such as shallow trench isolationregions, are formed in a semiconductor substrate 12.

In one embodiment, substrate 12 includes a single crystallinesemiconductor layer on at least its surface portion. The substrate 12may comprise a single crystalline semiconductor material such as, butnot limited to Si, Ge, SiGe, GaAs, InSb, GaP, GaSb, InAlAs, InGaAs,GaSbP, GaAsSb, and InP. In a certain embodiment, the substrate 12 ismade of Si.

The isolation insulating layer 14 includes one or more layers of aninsulating material. The insulating material for the insulating layer 14may include silicon oxide, silicon nitride, silicon oxynitride (SiON),SiOCN, fluorine-doped silicate glass (FSG), or a low-k dielectricmaterial, formed by LPCVD, PECVD or flowable CVD. An anneal operationmay be performed after the formation of the isolation insulating layer14. In some embodiments, the isolation insulating material extends overthe uppermost surface of the substrate, and a planarization operation,such as a chemical mechanical polishing (CMP) method and/or an etch-backmethod, is subsequently performed to remove the upper portion of theisolation insulating layer.

A portion of the semiconductor substrate 12 is removed between adjacentisolation insulating layers 14 to form a recess 16, as shown in FIG. 2.In some embodiments, the removed portion of the semiconductor substrateis removed by suitable photolithographic and etching operations. Thedepth D1 of the recess from an upper surface of the isolation insulationlayer 14 to the upper surface of the recessed substrate 12 is about 1 toabout 200 nm in some embodiments.

A first semiconductor layer 18 is formed in the recess 16 and a secondsemiconductor layer 20 is formed over the first semiconductor layer 18,as shown in FIG. 3. In certain embodiments, the upper surface of thesecond semiconductor layer 20 extends above the upper surface of theisolation insulating layer 14, as shown in FIG. 4. A gate electrodestructure, including a gate dielectric layer 22 and gate electrode layer24 are subsequently formed over the second semiconductor layer 20.

The first semiconductor layer 18 may include one or more layers of suchas, but not limited to, Si, Ge, SiGe, SiGeSn, GeSn, GaAs, InSb, GaP,GaSb, InAlAs, InGaAs, GaSbP, GaAsSb, and InP. In some embodiments, thefirst semiconductor layer 18 is a buffer layer. Buffer layers are usedto transition between the crystal lattice of the semiconductor substrateand the crystal lattice of the second semiconductor layer in someembodiments. The second semiconductor 20 is an alloy semiconductorlayer, and may include one or more layers of such as, but not limitedto, SiGe, SiGeSn, GeSn, GaAs, InSb, GaP, GaSb, InAlAs, InGaAs, GaSbP,GaAsSb, and InP. In some embodiments, the first semiconductor layer 18is Ge and the second semiconductor layer 20 is GeSn. The GeSn in thesecond semiconductor layer 20 is Ge_(1-x)Sn_(x), where 0.05≤x≤0.2, insome embodiments. In certain embodiments, the alloy semiconductormaterial is selected from the group consisting of Ge_(0.95)Sn_(0.05),Ge_(0.922)Sn_(0.0728), Ge_(0.90)Sn_(0.10), Ge_(0.95)Sn_(0.05),Ge_(0.83)Sn_(0.17), and Ge_(0.80)Sn_(0.20).

In certain embodiments, the first and second semiconductor layers 18, 20are doped with up to 2×10²⁰ dopants/cm³. The dopants can be n-type orp-type dopants, including one or more of As, Sb, P, B, Ga, and Al. Insome embodiments, in-situ doping is used to incorporate the dopant intothe semiconductor region. In other embodiments, ion-implantation,plasma-doping, solid-phase doping, or other doping techniques are used.

In some embodiments, the first semiconductor layers 18 and secondsemiconductor layers 20 are epitaxially formed over the substrate 12. Insome embodiments, the thickness of the first semiconductor layer 18 isabout 1 micron or less. In certain embodiments, the first semiconductorlayer 18 is not formed. In some embodiments, the thickness of the secondsemiconductor layer 20 is in a range from about 1 nm to about 200 nm.

The first and second semiconductor layers 18, 20 may be formed bychemical vapor deposition (CVD), including metal-organic CVD (MOCVD),low pressure CVD (LPCVD) and plasma enhanced CVD (PECVD), physical vapordeposition (PVD), molecular beam epitaxy (MBE), atomic layer deposition(ALD), or other suitable processes.

In certain embodiments, the gate dielectric layer 22 includes one ormore layers of a dielectric material, such as silicon oxide, siliconnitride, or high-k dielectric material, other suitable dielectricmaterial, and/or combinations thereof. Examples of high-k dielectricmaterial include HfO₂, HfSiO, HfSiON, HfTaO, HfTiO, HfZrO, zirconiumoxide, aluminum oxide, titanium oxide, hafnium dioxide-alumina(HfO₂—Al₂O₃), other suitable high-k dielectric materials, and/orcombinations thereof. In some embodiments, the gate dielectric layer 22includes an interfacial layer (not shown) formed between the nanowiresand the dielectric material. The gate dielectric layer 22 may be formedby CVD, ALD, or other suitable methods. The thickness of the gatedielectric layer 22 is in a range from about 1 nm to about 6 nm in someembodiments.

The gate electrode layer 24 includes one or more layers of a reflectiveconductive material, such as a metal, including: aluminum, copper,titanium, tantalum, tungsten, cobalt, molybdenum, nickel, alloysthereof, and other suitable materials, and/or combinations thereof. Thegate electrode layer 24 may be formed by CVD, ALD, PVD, electroplating,or other suitable methods.

In certain embodiments of the present disclosure, one or more workfunction adjustment layers (not shown) are interposed between the gatedielectric layer 22 and the gate electrode 24. The work functionadjustment layers are made of a conductive material such as a singlelayer of TiN, TaN, TaAlC, TiC, TaC, Co, Al, TiAl, HfTi, TiSi, TaSi orTiAlC, or a multilayer of two or more of these materials. For an nFET,one or more of TaN, TaAlC, TiN, TiC, Co, TiAl, HfTi, TiSi and TaSi isused as the work function adjustment layer, and for a pFET, one or moreof TiAlC, Al, TiAl, TaN, TaAlC, TiN, TiC and Co is used as the workfunction adjustment layer. The work function adjustment layer may beformed by ALD, PVD, CVD, e-beam evaporation, or other suitable process.Further, the work function adjustment layer may be formed separately forthe nFET and the pFET, which may use different metal layers.

In some embodiments, the gate electrode structure is formed overlyingthe channel region of the semiconductor device and source/drain regionsare formed on opposing sides of the channel region. Source/drain regionsis used in this disclosure to designate source regions, drain regions,or both source and drain regions.

Adverting to FIG. 5, in some embodiments, the semiconductor device 10 isexposed to radiation 26. The exposure to radiation providesultra-short-time and high-temperature annealing in some embodiments. Asshown in FIG. 5, the reflective gate electrode 24 reflects the radiation26, while the radiation 26 is absorbed by the regions of thesemiconductor device 10 not covered by the reflective gate electrode 24.The second semiconductor layer 20 is annealed by the absorbed radiation26.

In some embodiments, the radiation source is a laser or a flash lamp,including argon and xenon flash lamps. The semiconductor device 10 isexposed to the radiation 26 for a period of time ranging from greaterthan 0 s to about 100 ms. In particular, each portion of the secondsemiconductor layer 20 not covered by the reflective gate electrode 24is exposed to the radiation is exposed for a period of time ranging fromgreater than 0 s to about 100 ms. In certain embodiments, each portionof the second semiconductor layer 20 exposed to the radiation 26 isexposed for about 1 ns to about 1 ms. In other embodiments, each portionof the second semiconductor layer 20 exposed to the radiation 26 isexposed for about 5 ns to about 100 μs. In other embodiments, eachportion of the second semiconductor layer 20 exposed to the radiation 26is exposed for about 10 ns to about 100 ns. During the exposure toradiation, the exposed portions of the semiconductor device 10 undergoultra-rapid heating and reach temperatures of up to 2000° C. In otherembodiments, the exposed portions of the semiconductor device 10 reachtemperatures up to 1100° C.

In some embodiments, the power density of the radiation 26 is about 1mJ/cm² to about 900 mJ/cm². In certain embodiments, the power density ofthe radiation 26 ranges from about 250 mJ/cm² to about 300 mJ/cm². Incertain embodiments, dynamic surface annealing occurs during theexposure to radiation. In dynamic surface annealing, the activation ofthe doped regions of the exposed semiconductor layer occurs withoutdiffusion of the dopants.

In some embodiments, the radiation 26 is laser radiation, and the secondsemiconductor layer 20 undergoes laser annealing as a result of theexposure to the laser radiation 26. In some embodiments, the wavelengthused in laser annealing is about 193 nm to about 2296 nm (λ=2296 isequivalent to the bandgap of Ge_(0.90)Sn_(0.10)). In other embodiments,the wavelength used in laser annealing is about 193 nm to about 1878 nm(=1878 nm is equivalent to the bandgap of Ge). In certain embodiments, alaser beam having a wavelength of about 532 nm is used. In someembodiments, the power density used in laser annealing is about 1 mJ/cm²to about 900 mJ/cm². In some embodiments, the full-width-at-half-maximum(FWHM) of the laser pulse is about 1 ns to about 1 ms. A particular spoton the second semiconductor layer is exposed to the laser beam fromabout 10 ns to about 100 μs in some embodiments. The shape of laser beamcan be any shape including linear, elliptical, circular, etc.

For example, in some embodiments a particular spot on the secondsemiconductor layer is exposed to the laser beam for 15 μs when a laserpulse having a FWHM=12 ns, repetition frequency f=50 kHz, a relativevelocity between substrate and the laser beam is 0.6 cm/s, and laserspot size of 150 μm, as shown in the following calculations:

150 μm/0.6 cm/s=0.025 s, 0.025 s x 50 kHz=1,250, and 1,250×12 ns=15 μs.

In another embodiment, a particular spot on the second semiconductorlayer is exposed to the laser beam for 12 ns when a laser pulse having aFWHM=4 ns, repetition frequency f=1 Hz, a relative velocity between thesubstrate and the laser beam of 0.1 cm/s, and laser spot size of 3 mm,as shown in the following calculations:

3 mm/0.1 cm/s=3 s,3 s×1 Hz=3, and 3×4 ns=12 ns.

The laser beam may be scanned across the surface of the semiconductordevice 10. In some embodiments, the laser beam is stationary while astage carrying the semiconductor device moves. The velocity of the stagecarrying the semiconductor devices during laser annealing is 0 to about100 cm/s in some embodiments. In other embodiments, the laser beam isscanned over the surface of the semiconductor device while the stage isstationary. The velocity of the laser beam incident to the semiconductordevice during laser annealing is 0 to about 100 cm/s in someembodiments.

In some embodiments, flash annealing is used. In some embodiments, flashannealing is provided by exposing the semiconductor device 10 toradiation from a flash lamp, including an argon flash lamp or a xenonflash lamp. In some embodiments, the semiconductor device 10 is heatedto a temperature ranging from about 300° C. to about 600° C. beforeexposure to the radiation 26. In certain embodiments, the semiconductordevice 10 is heated to a temperature ranging from about 400° C. to about450° C. before exposure to the radiation 26. The semiconductor device 10is exposed to the flash radiation 26 for a period of time ranging fromabout 0.1 ms to about 100 ms. In certain embodiments, the semiconductordevice 10 is exposed to flash radiation 26 for about 0.5 ms to about 1.5ms. During the exposure to radiation, the exposed portions of thesemiconductor device 10 undergo ultra-rapid heating and reachtemperatures of up to 2000° C. In other embodiments, the exposedportions of the semiconductor device 10 reach temperatures ranging fromabout 800° C. to about 1100° C. during flash annealing. In someembodiments, the power density of the radiation 26 is about 1 mJ/cm² toabout 900 mJ/cm². In certain embodiments, the power density of theradiation 26 ranges from about 250 mJ/cm² to about 300 mJ/cm².

The annealing operation transforms the second semiconductor layer 20 sothat a surface region 28 of the unmasked portion of the secondsemiconductor layer has a higher concentration of a second alloy elementof the alloy material of the second semiconductor layer than an internalregion of the unmasked portion of the second semiconductor layer 38. Asshown in FIG. 6, the surface region 28 of the unmasked portion of thesecond semiconductor layer surrounds the internal region 38 of theunmasked portion of the second semiconductor layer. In some embodiments,the radiation annealing causes the second alloy element of thesemiconductor alloy to migrate to the surface region of the secondsemiconductor layer and form islands of higher concentration secondalloy element on the surface of the second semiconductor alloy. Thesurface region 28 with a higher concentration islands/layer of thesecond element of the alloy material may have improved contactresistivity.

When the second semiconductor layer 20 is GeSn, the channel region underthe gate electrode structure is represented as Ge_(1-y)Sn_(y), theSn-rich surface region 28 is represented as Ge_(1-w)Sn_(w), and theinterior portion with reduced Sn content is represented asGe_(1-x)Sn_(x), where x<y<w. When x<y, the internal region 38 inducestensile strain in the channel region, thereby improving electronmobility in the channel region of n-type FETs.

The thickness of the surface region 28 of the second semiconductor layeris about 1 to about 20 nm in some embodiments.

In certain embodiments, the annealing operation transforms GeSnsource/drain regions into a GeSn region with a reduced Sn content and aGeSn nFET stressor. Further, using selective laser annealing accordingto embodiments of the present disclosure, allows a higher dopantconcentration of n-type dopant, such as >3×10¹⁹ cm⁻³, to be achieved inthe GeSn source/drain regions. Because of the nanosecond-scale annealingduration, laser annealing causes the semiconductor layer to becomesupersaturated in certain embodiments (i.e.—the solute is the dopant andthe solvent is the semiconductor material). The semiconductor layerbecomes metastable and the dopant concentration increases. In addition,laser annealing effectively activates dopants in the source/drainregions in some embodiments.

Adverting to FIG. 7, in some embodiments of the disclosure, insulatingsidewalls 30 are formed on lateral surfaces of the gate electrodestructure, and an interlayer dielectric 32 is formed overlying thesemiconductor device 10. The interlayer dielectric is a spin on glass(SOG), including phosphosilicate glass (PSG) or borophosphosilicateglass (BPSG), in some embodiments. The insulating sidewalls 30 may beformed of an oxide, such as silicon oxide, and/or a nitride, such assilicon nitride. The thickness of the insulating sidewalls 30 is 10 nmto about 200 nm in some embodiments. Vias are subsequently formed in theinterlayer dielectric 32, such as by using suitable photolithographic,etching, and material deposition techniques, and electrical contacts 36are formed in the vias providing electric contact to the source/drainstressors 28 and gate electrode layer 24. In some embodiments, a contactbarrier liner layer 34 is formed in the via prior to forming the contact36. In some embodiments, the contact barrier liner layer 34 is formed ofa metal nitride, such as TaN or TiN. The contact barrier liner layer maybe formed by ALD, PVD, CVD, or other suitable process. In someembodiments, the contact 36 is formed of aluminum, copper, titanium,tantalum, tungsten, cobalt, molybdenum, nickel, alloys thereof, andother suitable conductive materials. The contact 36 may be formed byCVD, ALD, electroplating, or other suitable methods.

In some embodiments, the first semiconductor layer 18 is a buffer layer.In certain embodiments, a Si_(a)Ge_(b)Sn_(1-a-b) single layer, multiplelayer, or graded buffer layer 18 is formed on the substrate 12 having athickness of about 0 to about 10 μm. In certain embodiments, no bufferlayer is included. Rather, only one semiconductor layer 20 including analloy semiconductor material is formed on the substrate 12 as shown inFIG. 8. In some embodiments, such as when a Ge substrate is used, abuffer layer is not used. The operations for forming the embodiment ofFIG. 8, are the same as those described with respect to FIGS. 4-7.

FIGS. 9-11 are cross-sectional views of exemplary sequential operationsin a method of manufacturing a semiconductor device 10 according toanother embodiment of the present disclosure. As shown in FIG. 9, asemiconductor device 10 having a gate electrode structure formed over asemiconductor layer 20 is exposed to radiation 26, such as laserradiation. The semiconductor device 10 is exposed to radiation 26 for alonger period of time than the embodiments described in FIGS. 1-8. Insome embodiments, each portion of the second semiconductor layer 20 notcovered by the reflective gate electrode 24 is exposed to the radiationfor a period of time ranging from about 1 s to about 100 s. In certainembodiments, each portion of the second semiconductor layer 20 notcovered by the reflective gate electrode 24 is exposed to the radiation26 for a period of time ranging from about 5 s to about 50 s. Theexposure radiation transforms the first semiconductor layer 18 and thesecond semiconductor layer 20 so that a surface region 28 of a portionof the first and second semiconductor layers 18, 20 not masked by thegate electrode 24 has a higher concentration of the second element thanan internal region 38 of a portion of the first and second semiconductorlayers 18, 20 not masked by the gate electrode 24 in some embodiments.In some embodiments, the longer duration of exposure to radiation 26causes the surface region 28 of the unmasked portion of the secondsemiconductor layer having a higher concentration of a second element ofthe alloy material of the second semiconductor layer and the internalregion of the unmasked portion of the second semiconductor layer 38 witha lower concentration of the second alloy material to extend a depth D2into the first semiconductor layer 18, as shown in FIG. 10. In thisembodiment, the second element of alloy semiconductor layer 20 diffusesinto the first semiconductor layer 18, during the annealing operation.For example, when the first semiconductor layer 18 is a Ge layer and thesecond semiconductor layer 20 is a GeSn layer, in addition to the Snmigrating to the surface of the GeSn layer, Sn also migrates into the Gelayer, thereby extending the GeSn layer into the Ge layer. As depictedin FIG. 11, an interlayer dielectric 32, and liner layer 34 and contacts36 in the interlayer dielectric are subsequently formed, as describedherein with respect to FIG. 7.

FIGS. 12-14 are cross-sectional views of exemplary sequential operationsin a method of manufacturing a semiconductor device 10 according toanother embodiment of the present disclosure. As shown in FIG. 12, aninsulating sidewall 30 is formed on sidewalls of the gate structure, anda reflective metal sidewall spacer 40 is formed over the insulatingsidewall 30. After forming the pair of sidewalls 30, 40, thesemiconductor device is exposed to radiation 26 to anneal the secondsemiconductor layer 20 to form surface portions 28 having a higherconcentration of the second element of the alloy semiconductor materialthan the interior portion 38 of the second semiconductor layer, as shownin FIG. 13. The reflective metal sidewall spacer 40 reduces the portionof the second semiconductor layer 20 that is exposed to radiation andthus reduces the size of the surface portion 28 and interior portion 38,thereby reducing the size of the source/drain regions relative to thechannel region. As depicted in FIG. 14, an interlayer dielectric 32, andliner layer 34 and contacts 36 in the interlayer dielectric aresubsequently formed, as described herein with respect to FIG. 7.

The reflective metal sidewall spacers 40 can be used to reduce the sizeof the source/drain regions and extend the channel region, or to preventheating of the channel region during the irradiation operation. Thereflective metal sidewall spacers 40 may be formed of any of the metalsdisclosed herein for use in the gate electrode layer 24, includingaluminum, copper, tantalum, tungsten, cobalt, molybdenum, nickel, andalloys thereof.

FIGS. 15-17 are cross-sectional views of exemplary sequential operationsin a method of manufacturing a semiconductor device 10 according toanother embodiment of the present disclosure. Adverting to FIG. 15, asurface portion 28 of the second semiconductor layer having a higherconcentration of a second element of the alloy material of the secondsemiconductor layer than an interior portion of the second semiconductorlayer 38, is formed in the same manner as the embodiment described inFIGS. 3-6.

The surface portion 28 is subsequently removed exposing interior portion38, as shown in FIG. 16. The surface portion 28 is removed by etchingusing an appropriate etchant that is selective to the surface portionhaving the higher concentration of the second element of the alloymaterial than the interior portion. In certain embodiments, the etchantis 5%-37% HCl or 10%-30% H₂O₂.

A metal contact layer 42 is subsequently formed over the interiorportion 38 of the second semiconductor layer, as shown in FIG. 17. Insome embodiments, the metal contact layer 42 includes Ni, Ti, Pt, Co orany alloy of these four elements. The metal contact layer 42 is formedby CVD, ALD, electroplating, or other suitable methods. In someembodiments, the portion of the metal contact layer 42 contacting theinterior portion 38 of the second semiconductor layer may react or forman alloy with the interior portion 38 second semiconductor layer at theinterface between the metal contact layer 42 and the interior portion 38of the second semiconductor layer.

FIGS. 18-22 are isometric views of exemplary sequential operations in amethod of manufacturing a complementary metal oxide semiconductor (CMOS)FinFET device 50 according to another embodiment of the presentdisclosure. As shown in FIG. 18, an n-type fin structure 56 and p-typefin structure 58 are formed on a semiconductor substrate 52 byoperations similar to those described herein with respect to FIGS. 1-3.An isolation insulating layer 54 is formed on the semiconductorsubstrate 52 surrounding the fin structures 56, 58.

A gate stack 60 including a gate dielectric layer and gate electrodelayer are formed overlying a channel region of the fin structures 56,58. Source/drain regions 62, 64 are epitaxially formed on the finstructures 56, 58 on opposing sides of the gate structure 60, in someembodiments forming an n-type FET (nFET) 57 and a p-type FET (pFET) 59,as shown in FIG. 19. The source/drain regions 62, 64 are epitaxiallyformed alloy semiconductors, and may include one or more layers of suchas, but not limited to, SiGe, SiGeSn, GeSn, GaAs, InSb, GaP, GaSb,InAlAs, InGaAs, GaSbP, GaAsSb, and InP. The nFET source/drain regions 62are doped with an n-type dopant, such as As, P, or Sb, and the pFETsource/drain regions 64 are doped with p-type dopants, such as B, Al,and Ga.

A mask 66 is subsequently formed over the pFET 59, as shown in FIG. 19.The mask is a reflective material, such as a metal. Any suitablereflective metal, such as nickel, aluminum, tantalum, tungsten, andcopper, can be used as the mask 66. In certain embodiments, thethickness of the mask 66 ranges from about 20 nm to about 200 nm. Themask 66 is formed by CVD, ALD, electroplating, or other suitablemethods.

The CMOS device 50 is subsequently exposed to radiation 68, such aslaser radiation, as shown in FIG. 21. The radiation is absorbed by thesource/drain regions 62 of the nFET 57, and is reflected by the gatestructure 60 of the nFET 57 and mask 66 over the pFET 59, therebytransforming a surface portion of the source/drain regions 62 of thenFET to a surface portion 70 having a higher concentration of a secondelement of the alloy material than an interior portion of thesource/drain regions 62, as shown in FIG. 22.

In a certain embodiment, the n-type fin structure 56 is made ofGe_(1-y)Sn_(y) and the p-type fin structure 58 is made ofGe_(1-p)Sn_(p). The epitaxially formed source/drain regions 62, 64 aremade of Ge_(1-z)Sn_(z), where z>p. After exposure to radiation 68, thepFET source/drain region 64 is maintained as Ge_(1-z)Sn_(z) because thepFET was protected by the reflective mask 66 during radiation exposure68. The nFET source/drain region 62 has a surface portion 70, having anSn-rich composition Ge_(1-w)Sn_(w), where w>y; and an Sn-poor interiorportion having a composition Ge_(1-w)Sn_(x), where x<y. The Sn-poorinterior portion interior portion of the nFET source/drain region 62induces tensile strain in the channel region, thereby improving electronmobility in the channel region of n-type FETs.

FIGS. 23 to 30 are cross-sectional views of exemplary sequentialoperations in a method of manufacturing a semiconductor device 10according to another embodiment of the present disclosure. Isolationinsulating layers 14, such as shallow trench isolation regions, areformed in a semiconductor substrate 12, as shown in FIG. 23.

A portion of the semiconductor substrate 12 is removed between adjacentisolation insulating layers 14 to form a recess 16, as shown in FIG. 24.In some embodiments, the portion of the semiconductor substrate removedis removed by suitable photolithographic and etching operations. Thedepth D1 of the recess from an upper surface of the isolation insulationlayer 14 to the upper surface of the substrate 12 is about 1 to about200 nm in some embodiments.

A first semiconductor layer 18 is formed in the recess 16 and a secondsemiconductor layer 20 is formed over the first semiconductor layer 18,as shown in FIG. 25. In some embodiments, a planarization operation isperformed on the device, so that the upper surface of the isolationinsulating layer 14 is at the same level as the upper surface of thesecond semiconductor layer 20. The first and second semiconductor layers18, 20 are the same materials and are formed in the same manner as thefirst and second semiconductor layers 18, 20 in the embodimentsdescribed herein in reference to FIG. 3.

A reflective mask 72 is subsequently formed over the secondsemiconductor layer 20, as shown in FIG. 26, and the semiconductordevice is exposed to radiation 26, such as laser radiation. Any suitablereflective metal, such as nickel, aluminum, tantalum, tungsten, andcopper, can be used as the mask 72. In certain embodiments, thethickness of the mask 72 ranges from about 20 nm to about 200 nm. Themask 72 is formed by CVD, ALD, electroplating, or other suitablemethods. The reflective mask 72 reflects the radiation 26, while theradiation is absorbed by the regions of the semiconductor device 10 notcovered by the reflective mask 72. The second semiconductor layer 20 isannealed by the absorbed radiation 26.

In some embodiments, metal gate electrode and/or metal mask, in additionto blocking (reflecting) the radiation, also protects the gatedielectric, pFET, and/or channel region during the annealing.

The mask 72 is removed to expose the upper surface of the secondsemiconductor layer after the irradiation operation, as shown in FIG.27. As described herein, the annealing operation transforms the secondsemiconductor layer so that a surface portion 28 of the secondsemiconductor layer includes a layer or islands having a higherconcentration of a second element of the alloy material of the secondsemiconductor layer than an interior portion of the second semiconductorlayer 38.

The isolation insulating layers 14 are subsequently recess etched insome embodiments exposing at least a portion of the side surface of thesurface portion 28 of the second semiconductor layer, as shown in FIG.28.

A gate electrode structure including, a gate dielectric layer 22 and agate electrode layer 24, is subsequently formed on the channel region ofthe second semiconductor layer 20, as shown in FIG. 29. The gatedielectric layer 22 and the gate electrode layer 24 are formed of thesame material and in the same manner described herein with respect tothe embodiment of FIG. 4.

Adverting to FIG. 30, in some embodiments of the disclosure, insulatingsidewalls 30 are formed on lateral surfaces of the gate electrodestructure, and a interlayer dielectric 32 is formed overlying thesemiconductor device 10. In some embodiments, a contact barrier linerlayer 34 is formed in the via prior to forming the contact 36. Theinsulating sidewalls 30, interlayer dielectric 32, contacts 36, andcontact barrier liner layers 34 are formed of the same material and inthe same manner as described herein with respect to the embodiment ofFIG. 7.

FIGS. 31-35 are isometric views of exemplary sequential operations in amethod of manufacturing a complementary metal oxide semiconductor (CMOS)device 80 according to another embodiment of the present disclosure. Asshown in FIG. 31, an n-type fin structure 86 and p-type fin structure 88are formed on a semiconductor substrate 82. An isolation insulatinglayer 84 is formed on the semiconductor substrate 82 surrounding the finstructures 86, 88. In some embodiments, the device is planarized, suchas by CMP, so that the upper surfaces of the fin structures 86, 88 andthe upper surface of the isolation insulating layer 84 are substantiallycoplanar.

A mask 90 is subsequently formed over the p-type fin structure 88 and achannel region n-type fin structure 86, as shown in FIG. 32. The mask isa reflective material, such as a metal. Any suitable reflective metal,such as nickel, aluminum, tantalum, tungsten, and copper, can be used asthe mask 90. In certain embodiments, the thickness of the mask 90 rangesfrom about 20 nm to about 200 nm. The mask 90 is formed by CVD, ALD,electroplating, or other suitable methods.

The CMOS device 80 is subsequently exposed to radiation 92, such aslaser radiation, as shown in FIG. 33. The radiation is absorbed by theexposed source/drain regions 87 of the n-type fin structure 86, and isreflected by the reflective mask 90, thereby transforming a surfaceportion of the source/drain regions 87 of the nFET to a surface portion94 having a higher concentration of a second element of the alloymaterial than an interior portion of the source/drain regions 87, asshown in FIG. 34. FIG. 34 shows the structure of the CMOS device 80after the isolation insulating layer 84 is recessed. The isolationinsulating layer 84 is recessed by an etch back operation in someembodiments.

A gate stack 96, including a gate dielectric layer and gate electrodelayer, is formed overlying a channel region of the fin structures 86,88. Source/drain regions 87, 89 are formed on the fin structures 86, 88on opposing sides of the gate structure 96, in some embodiments, formingan n-type FET (nFET) 97 and a p-type FET (pFET) 99, as shown in FIG. 35.

In some embodiments, the radiation annealing causes the second alloyelement of the semiconductor alloy to migrate to the surface of thesemiconductor alloy and form islands of higher concentration secondalloy element on the surface of the second semiconductor alloy. As shownin a plan view of a gate structure/fin structure detail of asemiconductor device 100 (FIG. 36) according to some embodiments, a gateelectrode 104 has source/drain regions 106 formed on opposing sides ofthe gate electrode 104. An isolation insulating region 102 surrounds thegate electrode 104 and source/drain regions 106. Laser annealing in someembodiments forms islands 110 of higher concentration of the secondalloy element of the semiconductor alloy on the surface of thesource/drain regions 106. Laser annealing also forms a stripe-like roughsurface on the surface of the source/drain regions 106, as illustratedby stripes 108 on the source/drain regions 106. The scanning laser beammay produce the stripe-like or rough surface because not every point onthe surface may receive the same amount of laser radiation. In otherembodiments, the surface of the source/drain regions 106 is covered witha more evenly distributed surface layer of increased concentration ofthe second alloy element of the source/drain semiconductor alloy, asshown in FIG. 37.

FIGS. 38 and 39 illustrate the relationship between a wafer and a laserbeam (incident angle). As shown in FIGS. 38 and 39, the angle ofincidence α1, α2 of the laser beam irradiating the semiconductor devicevaries in different embodiments. As shown in FIG. 38, the angle ofincidence α1 in some embodiments is about 90°. The semiconductor devicesare formed on a wafer 122 in some embodiments. The wafer 122 is locatedon a stage 120 in this embodiment. In certain embodiments, the stage andradiation source are configured to tilt independently of each other, andthe stage or the radiation source is tilted so that an angle ofincidence of radiation from the radiation source θ1 from a horizontalorientation onto the surface region of the unmasked portion of the alloysemiconductor material layer is less than 90°. In certain embodiments,the stage 120 is tilted at an angle θ1 of about 0°, and the laser beam124 is focused by a lens 126. In other embodiments, the stage 120 istilted at an angle of θ2 from a horizontal orientation, and the laserbeam is tilted at an angle of incidence α2. In certain embodiments, thestage is tilted at an angle of 0°≤θ2≤60°. In certain embodiments, theangle of incidence of the laser beam is 0°≤α2≤60°. The laser beam andthe stage may be tilted in order to vary the amount of incident laserradiation that is absorbed or reflected by the semiconductor layers. Forexample, for a Ge layer on a Si layer, where the indices of refractionare n_(Ge)=4.999 and n_(Si)=4.142, being irradiated by a 532 nmwavelength laser, total reflection happens when the laser beam is tilted56°. In order to avoid undesirable total reflection, the angle ofincidence of the laser beam is 0°≤α2≤60° in order to avoid totalreflection (α2 needs to be lower than 56° in the case of Ge beingirradiated by a 532 nm wavelength laser on Si). When total reflectionhappens, the laser beam will propagate in the Ge layer on Si like awaveguide. In the case of total internal reflection, the region beingannealed cannot be controlled. So total reflection is undesirable.

In an exemplary embodiment, an nFET stressor region is formed in asemiconductor layer by subjecting a GeSn layer to laser annealing usinga laser with a wavelength of 532 nm, power density of 25 mJ/cm²,repetition rate of 50 kHz, FWHM of 12 ns, elliptical-shaped beam, with avelocity of wafer stage carrying the wafers of 6 cm/s and scanningvelocity of the laser beam of 0 cm/s. The exemplary nFET contains abuffer layer, a nFET S/D stressor comprising Ge_(1-x)Sn_(x) wherein0≤x<0.35, Ge_(1-y) Sn_(y) channel wherein x<y<0.35, and a Sn-richGe_(1-w)Sn_(w) island/layer on the nFET S/D stressor Ge_(1-x)Sn_(x),where x<y<w.

In an exemplary embodiment, after laser annealing an alloy semiconductorlayer having a composition of Ge_(0.83)Sn_(0.17), a surface layer havingSn-rich islands is provided having a composition of Ge_(0.66)Sn_(0.34),and the Sn-reduced interior stressor portion has a composition ofGe_(0.92)Sn_(0.08).

Embodiments of the disclosure provide the advantage of using a singlestep process, such as laser annealing, to activate dopants, form an S/Dstressor, and form a Sn-rich island/layer on the surface of the S/Dregions. The Sn-rich island/layer on the S/D regions provide reducedcontact resistance.

In an embodiment of the disclosure, a method of manufacturing asemiconductor device includes forming an alloy semiconductor materiallayer comprising a first element and a second element on a semiconductorsubstrate. A mask is formed on the alloy semiconductor material layer toprovide a masked portion and an unmasked portion of the alloysemiconductor material layer. The unmasked portion of the alloysemiconductor material layer not covered by the mask is irradiated withradiation from a radiation source to transform the alloy semiconductormaterial layer so that a surface region of the unmasked portion of thealloy semiconductor material layer has a higher concentration of thesecond element than an internal region of the unmasked portion of thealloy semiconductor material layer. The surface region surrounds theinternal region. In another embodiment of the disclosure, a method ofmanufacturing a semiconductor device includes forming a plurality ofisolation insulating layers in a semiconductor substrate, and removing aportion of the semiconductor substrate between adjacent spaced apartisolation insulating layers to form a recess. A first semiconductormaterial layer is formed in the recess. A second semiconductor materiallayer is formed on the first semiconductor material layer. The secondsemiconductor material is different from the first semiconductormaterial. The second semiconductor material is an alloy comprising afirst element and a second element different from the first element. Theinsulating layers are etched to recess the insulating layers below anupper surface of the second semiconductor material layer. A mask isformed on the second semiconductor material layer to provide a maskedportion and an unmasked portion of the second semiconductor materiallayer. The unmasked portion of the second semiconductor material layernot covered by the mask is irradiated with radiation from a radiationsource to transform the second semiconductor material layer so that asurface region of the unmasked portion of the second semiconductormaterial layer has a higher concentration of the second element than aninternal region of the second semiconductor material layer. The surfaceregion surrounds the internal region.

In another embodiment of the disclosure, a semiconductor device isprovided including a first semiconductor material layer disposed on asemiconductor substrate. A second semiconductor material layer isdisposed on the first semiconductor material layer. The secondsemiconductor material is formed of an alloy comprising a first elementand a second element, and the first semiconductor material and thesecond semiconductor material are different. A gate electrode structureis disposed on a first portion of the second semiconductor materiallayer. A surface region of a portion of the second semiconductormaterial layer not covered by the gate electrode structure has a higherconcentration of the second element than an internal region of theportion of the second semiconductor material layer not covered by thegate electrode structure.

The foregoing outlines features of several embodiments or examples sothat those skilled in the art may better understand the aspects of thepresent disclosure. Those skilled in the art should appreciate that theymay readily use the present disclosure as a basis for designing ormodifying other processes and structures for carrying out the samepurposes and/or achieving the same advantages of the embodiments orexamples introduced herein. Those skilled in the art should also realizethat such equivalent constructions do not depart from the spirit andscope of the present disclosure, and that they may make various changes,substitutions, and alterations herein without departing from the spiritand scope of the present disclosure.

What is claimed is:
 1. A semiconductor device, comprising: a first layercomprising a first semiconductor material disposed on a semiconductorsubstrate comprising Si; a second layer of a second semiconductormaterial disposed on the first layer, wherein the second semiconductormaterial is formed of an alloy comprising a first element and Sn, andthe first semiconductor material and the second semiconductor materialare different; and wherein a surface region of an end portion of thesecond layer at both ends of the second layer has a higher concentrationof Sn than an internal region of the end portion of the second layer,and wherein the surface region surrounds the internal region.
 2. Thesemiconductor device of claim 1, further comprising: two isolationinsulating layers disposed at least partially in the semiconductorsubstrate, wherein the first layer and the second layer are disposed ina recess between the two isolation insulating layers.
 3. Thesemiconductor device of claim 1, further comprising: a gate structuredisposed on a middle portion of the second layer between the both endsof the second layer, wherein the gate structure comprises a gatedielectric layer and a gate electrode layer.
 4. The semiconductor deviceof claim 1, further comprising: source and drain contacts disposed overthe surface region of the end portion of the second layer at oppositeends of the second layer.
 5. The semiconductor device of claim 3,wherein the middle portion comprises a tensile strained channel region.6. A semiconductor device, comprising: two isolation insulating layersdisposed at least partially in a semiconductor substrate comprising Siand Ge; and an alloy semiconductor material layer comprising Ge and Sndisposed on the semiconductor substrate in a recess between the twoisolation insulating layers; wherein a surface region of an end portionof the alloy semiconductor material layer at both ends of the alloysemiconductor material layer has a higher concentration of Sn than aninternal region of the end portion of the alloy semiconductor materiallayer; and wherein at both ends of the alloy semiconductor materiallayer, an Sn-rich region is disposed between the internal region of theend portion and a corresponding adjacent isolation insulating layer. 7.The semiconductor device of claim 6, further comprising: a gatestructure disposed on a middle portion of the alloy semiconductormaterial layer between the both ends of the second layer, wherein thegate structure comprises a gate dielectric layer and a gate electrodelayer.
 8. The semiconductor device of claim 6, further comprising:source and drain contacts disposed over the surface region of the endportion of the alloy semiconductor material layer at both ends of thealloy semiconductor material layer.
 9. The semiconductor device of claim6, further comprising: a buffer layer disposed between the alloysemiconductor material layer and the semiconductor substrate.
 10. Thesemiconductor device of claim 9, wherein the buffer layer comprises amaterial selected from the group consisting of Si, Ge, and SiGe.
 11. Thesemiconductor device of claim 10, wherein the semiconductor substratecomprises a semiconductor substrate material selected from the groupconsisting of Si, Ge, and SiGe, and wherein a material of thesemiconductor substrate is different from the material of the bufferlayer.
 12. The semiconductor device of claim 11, wherein the material ofthe buffer layer is germanium.
 13. The semiconductor device of claim 6,wherein the surface region surrounds the internal region.
 14. Thesemiconductor device of claim 7, wherein the middle portion comprises atensile strained channel region.
 15. A semiconductor device, comprising:a first layer comprising Ge disposed in a recess between two isolationinsulating layers that are at least partially in a semiconductorsubstrate; a second layer of a second semiconductor material disposedover the first layer, wherein the second semiconductor material isdifferent from Ge, and wherein the second semiconductor material is analloy comprising Ge and a second element different from Ge; and whereina second element-rich surface layer of an end portion of the secondlayer at both ends of the second layer has a higher concentration of thesecond element than an internal region of the end portion of the secondlayer, and wherein the second element-rich surface layer is disposedbetween the internal region of the end portion and at least one of thetwo isolation insulating layers.
 16. The semiconductor device of claim15, wherein second semiconductor material is an alloy semiconductormaterial selected from the group consisting of Ge_(0.922)Sn_(0.0728),Ge_(0.90)Sn_(0.10), and Ge_(0.95)Sn_(0.05).
 17. The semiconductor deviceof claim 15, wherein an upper surface of each of the two isolationinsulating layers is below an upper surface of the second layer.
 18. Thesemiconductor device of claim 15, further comprising: source and draincontacts disposed over the second element-rich surface layer of the endportion at opposite ends of the second layer.
 19. The semiconductordevice of claim 15, wherein at each end of the second layer, a secondelement-rich region is disposed between the internal region and anadjacent isolation insulating layer.
 20. The semiconductor device ofclaim 15, further comprising: a gate structure disposed over a middleportion of the second layer, wherein the gate structure comprises a gatedielectric layer and a reflective gate electrode layer that isreflective in a wavelength range between 193 nm and 2296 nm.